EP1944376B1 - Procédé de production d'un composé amide - Google Patents

Procédé de production d'un composé amide Download PDF

Info

Publication number
EP1944376B1
EP1944376B1 EP06811414.9A EP06811414A EP1944376B1 EP 1944376 B1 EP1944376 B1 EP 1944376B1 EP 06811414 A EP06811414 A EP 06811414A EP 1944376 B1 EP1944376 B1 EP 1944376B1
Authority
EP
European Patent Office
Prior art keywords
nitrile
compound
amide compound
microbial cell
concentration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP06811414.9A
Other languages
German (de)
English (en)
Other versions
EP1944376A1 (fr
EP1944376A4 (fr
Inventor
Hiroko Shibamoto
Toshikazu Aikawa
Teruo Arii
Masanori Muramoto
Takeshi Fukuda
Kiyoshi Ito
Takeya Abe
Souichi Hazama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Chemicals Inc
Original Assignee
Mitsui Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Chemicals Inc filed Critical Mitsui Chemicals Inc
Priority to EP16187709.7A priority Critical patent/EP3135767B1/fr
Publication of EP1944376A1 publication Critical patent/EP1944376A1/fr
Publication of EP1944376A4 publication Critical patent/EP1944376A4/fr
Application granted granted Critical
Publication of EP1944376B1 publication Critical patent/EP1944376B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/09—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an acyclic unsaturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14—Hydrolases (3)
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C12P13/02—Amides, e.g. chloramphenicol or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes

Definitions

  • the present invention relates to a method for producing an amide compound.
  • the present invention relates more particularly to methods for producing an amide compound and an amide-based polymer and further more particularly to a method for efficiently producing a corresponding amide compound from a nitrile compound in an aqueous medium by the use of a catalyst having a nitrile hydratase activity, and a method for producing an amide-based polymer of high quality from the amide compound.
  • nitrile hydratases having a nitrile hydration activity capable of converting a nitrile group into an amide group through hydration and there has been already disclosed a method for producing a corresponding amide compound from a nitrile compound by the use of the enzyme or a microbial cell containing the enzyme.
  • the production method is known to have benefits such as a high conversion and a high selectivity from the nitrile compound to the corresponding amide compound, compared to the conventional scientific methods.
  • Patent Document 2 it is well known that the activity deterioration of a nitrile hydratase is prevented by using a nitrile compound in which the concentration of the contained hydrocyanic acid is reduced.
  • Patent Document 3 a method in which the reaction is carried out by using a microbial cell crosslinked with glutaraldehyde
  • Patent Document 4 a method in which the reaction is carried out in the presence of a higher unsaturated fatty acid or its salt
  • Patent Document 5 a method in which the reaction is carried out by using a microbial cell processed with an organic solvent or a processed product thereof.
  • one of the main methods for producing acrylamide is a method of hydrating acrylonitrile.
  • a method of hydrating acrylonitrile with a metallic copper catalyst such as Raney copper or the like or a method of hydrating acrylonitrile by using a microbial cell containing a nitrile hydratase or a processed product of the microbial cell as a catalyst.
  • the method for producing acrylamide using the microbial cell containing the nitrile hydratase as a catalyst has attracted attention because the method has a high conversion and a high selectivity of acrylonitrile, compared to the conventional method of hydration using the metallic copper catalyst.
  • acrylamides obtained by such reactions are mainly used as a raw material for an acrylamide-based polymer.
  • the applications of an acrylamide-based polymer include a flocculant.
  • the acrylamide-based polymer used as a flocculant is expected to have a higher molecular weight while maintaining the water solubility to improve the performance.
  • the acrylamide-based polymer is used as an additive for manufacturing paper, and the like, and, as the additive for manufacturing paper, a polymer being more excellent in hue is required in order to further improve the quality of the resulting paper.
  • the productivity of the amide compound using the nitrile hydratase is decreased due to other factors that are not be resolved by the conventional techniques described in the background art, and it has also been desired to resolve the factors in order to efficiently produce the amide compound using the nitrile hydratase.
  • an object of the invention is to provide a method for efficiently producing a corresponding amide compound from a nitrile compound by a reaction using a nitrile hydratase.
  • another object of the first invention is to provide a method for producing an amide-based polymer with high quality using the amide compound produced by the above method.
  • the present inventors have earnestly studied on the production method for an amide compound in order to solve the above problems of the invention.
  • the present inventors have found that, in a method for producing a corresponding amide compound from a nitrile compound in an aqueous medium using a catalyst having a nitrile hydratase activity, the amide compound may be efficiently produced without reducing the reaction rate of the nitrile hydratase when the concentration of benzene in the aqueous medium is reduced to a specific value or lower.
  • benzene in the aqueous medium is derived from the nitrile compound that is a raw material.
  • the amide compound may be efficiently produced by reducing the concentration of benzene to the same level as the above.
  • an amide-based polymer excellent in hue may be obtained by using the amide compound produced by the above method, under the reaction conditions in which the concentration of benzene is reduced as described.
  • the invention is as follows.
  • a corresponding amide compound in the reaction using a nitrile hydratase, a corresponding amide compound may be efficiently produced from a nitrile compound by reducing the concentration of benzene in an aqueous medium containing the nitrile compound to the specific value or lower.
  • an amide-based polymer excellent in hue may be obtained by using the amide compound produced by the above method, under the reaction conditions in which the concentration of benzene is reduced as described.
  • a catalyst having a nitrile hydratase activity used in the invention is a microbial cell producing a nitrile hydratase or a processed product of the microbial cell.
  • nitrile hydratase here is a protein having an ability of hydrating a nitrile compound.
  • the microbes producing a nitrile hydratase include microbes belonging to Nocardia, Corynebacterium, Bacillus, thermophilic Bacillus, Pseudomonas, Micrococcus, Rhodococcus represented by rhodochrous species, Acinetobacter, Xanthobacter, Streptomyces, Rhizobium, Klebsiella, Enterobacter, Erwinia, Aeromonas, Citrobacter, Achromobacter, Agrobacterium, Pseudonocardia represented by thermophila species, Bacteridium, Brevibacterium and the like.
  • Preferable are microbes belonging to Pseudonocardia and Rhodococcus and especially preferable are Pseudonocardia thermophila JCM3095 and Rhodococcus rhodochrous J-1.
  • the microbes producing the nitrile hydratase in the invention also include a transformant obtained by expressing a nitrile hydratase gene cloned from the above-mentioned microbe in an arbitrary host.
  • the arbitrary hosts referred to herein are not particularly limited, and include Escherichia coli as a representative example as in the case of Examples described later, Bacillus such as Bacillus subtilis and the like and other macrobial strains such as yeasts, Actinomyces and the like.
  • Examples thereof include MT-10822 (the strain deposited at National Institute of Bioscience and Human Technology, Agency of Industrial Science and Technology, Ministry of International Trade and Industry, 1-3, Higashi 1-chome, Tsukuba-shi, Ibaraki-ken, Japan on February 7th, 1996, under an accession number FERM BP-5785, under the terms of the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure).
  • the microbes producing the nitrile hydratase in the invention also include transformants expressing a mutant nitrile hydratase that are obtained by replacing, deleting, eliminating or inserting one or two or more of constituent amino acids of the enzyme with other amino acids by using recombinant DNA technology and thereby have been further improved in amide compound resistance, nitrile compound resistance and temperature resistance.
  • the microbial cell or the processed product of the microbial cell is generally used.
  • the microbial cell may be prepared by using a general method well known in the fields of molecular biology, bioengineering and genetic engineering. For example, there may be mentioned a method in which the microbe is planted in typical liquid culture mediums such as an LB medium, an M9 medium and the like and then is grown at an appropriate culture temperature (which is generally from 20°C to 50°C, and may be 50°C or higher in the case of a thermophilic bacterium), and the microbe is separated and recovered from the culture liquid using a centrifugal separation.
  • typical liquid culture mediums such as an LB medium, an M9 medium and the like
  • an appropriate culture temperature which is generally from 20°C to 50°C, and may be 50°C or higher in the case of a thermophilic bacterium
  • the processed products of the microbial cells are not particularly limited in the shape and include an extract and a ground product of the above microbial cell; a post-separated product obtained by separating and purifying a nitrile hydratase active fraction of the extract and the ground product; and an immobilized product obtained by immobilizing the microbial cell, or the extract, the ground product or the post-separated product of the microbial cell using an appropriate carrier.
  • These are usable as the processed product of the microbial cell in the invention as long as they have the nitride hydratase activity.
  • the microbial cell producing the nitrile hydratase or the processed product of the microbial cell may be used for the reaction immediately after production, or may be stored after production and used as needed.
  • the microbial cell producing the nitrile hydratase or the processed product of the microbial cell in the invention may be used in either a batch reaction or a continuous reaction.
  • the reactor type may be selected from a suspended bed, a fixed bed, a fluidized bed or the like, depending on the form of the microbial cell or the processed product of the microbial cell.
  • the concentration of catalyst in the reaction solution is not particularly limited as long as it does not disturb the mixing of an aqueous medium and the nitrile compound.
  • the aqueous medium in the invention refers to water or an aqueous solution (the whole reaction solution) in which there are dissolved a buffer agent such as a phosphate, an inorganic salt such as a sulfate or carbonate, a hydroxide of alkali metal, the amide compound, the nitrile compound, the catalyst having a nitrile hydratase activity at a suitable concentration.
  • a buffer agent such as a phosphate, an inorganic salt such as a sulfate or carbonate, a hydroxide of alkali metal, the amide compound, the nitrile compound, the catalyst having a nitrile hydratase activity at a suitable concentration.
  • the whole solution is defined as the aqueous medium.
  • the aqueous medium in the invention is also referred to as "the aqueous medium (I)".
  • a suitable mixing apparatus such as a rotary blade, a line mixer.
  • the concentration of the nitrile compound in the aqueous medium (I) during the reaction is not particularly limited as long as the reaction rate is not reduced by the concentration of benzene in the aqueous medium (I) or as long as the nitrile hydratase is not deactivated by the nitrile compound.
  • the percent by weight of the nitrile compound is preferably 50% by weight or less.
  • the nitrile compound used in the invention is not particularly limited as long as it is a compound that may be converted to an amide compound by the catalyst having the nitrile hydratase activity in the aqueous medium (I).
  • the representative examples preferably include nitrile compounds having 2 to 4 carbon atoms such as acetonitrile, propionitrile, acrylonitrile, methacrylonitrile, n-butyronitrile, isobutyronitrile, crotononitrile, ⁇ -hydroxyisobutyronitrile. More preferably acrylonitrile and methacrylonitrile are used.
  • benzene is contained in a commercially available acrylonitrile product because the acrylonitrile product is industrially produced by ammoxidation of propylene that contains a small amount of benzene.
  • the concentration of benzene contained in the aqueous medium (I) may be such that the reduction of the reaction rate is prevented and typically is 4.0 ppm or less and preferably is 2.2 ppm or less.
  • the words the reduction of the reaction rate is prevented mean that the reaction rate is 80% or more relative to the reaction rate (100%) achieved when the benzene concentration in the aqueous medium (I) is not more than 2 . 2 ppm.
  • the phrase "the concentration of benzene contained in the aqueous medium (I) is 4.0 ppm or less” means that the amount of benzene contained in 1 kg of the aqueous medium (I) is 4 mg or less. Benzene is removed from the nitrile compound by an adsorption treatment with activated carbon.
  • the reaction in the invention is typically carried out under normal pressure and may be carried out under pressure in order to increase the solubility of the acrylic compound in the aqueous medium (I).
  • the reaction temperature is not particularly limited and preferably is in a temperature range in which the nitrile hydratase is not deactivated and more preferably 0 to 50°C.
  • pH is not particularly limited as long as the nitrile hydratase activity is maintained and preferably is in the range of pH 5 to pH 10.
  • the amide-based polymer may be produced by homopolymerizing the amide compound obtained as mentioned above or by copolymerizing the amide compound with at least one unsaturated monomer copolymerizable with the amide compound.
  • the amide compound is acrylamide or methacrylamide obtained by the production method for the amide compound of the invention.
  • the unsaturated monomers copolymerizable with an amide compound include an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid, and a salt thereof; vinylsulfonic acid, styrene sulfonic acid, acrylamidemethylpropane-sulfonic acid, and a salt thereof; an alkylaminoalkyl ester of (meth)acrylic acid such as N,N-dimethylaminoethylmethacrylate, N,N-diethylaminoethylmethacrylate, N,N-dimethylaminoethylacrylate, and a quaternary ammonium derivative thereof; N,N-dialkylaminoalkyl(meth)acrylamide such as N,N-dimethylaminopropylmethacrylamide or N,N-dimethylaminopropylacrylamide and, a quaternary ammonium derivative thereof;
  • These monomers may be used alone or two or more kinds in combination.
  • the polymerization methods for these monomers include, for example, an aqueous solution polymerization, an emulsion polymerization.
  • the total concentration of the amide compound and the optional unsaturated monomer is typically 5 to 90% by weight.
  • a radical polymerization initiator may be used.
  • radical polymerization initiators there may be mentioned a peroxide such as potassium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide ; an azo-based free radical initiator such as azobisisobutyronitrile, 2,2'-azobis(4-amidinopropane) dihydrochloride, sodium 4,4'-azobis(4-cyanovalerate); and a so-called redox catalyst comprising the above-mentioned peroxides and reducing agents such as sodium bisulfite, triethanolamine, ammonium ferrous sulfate.
  • a peroxide such as potassium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide
  • an azo-based free radical initiator such as azobisisobutyronitrile, 2,2'-azobis(4-amidinopropane) dihydrochloride, sodium 4,4'-azobis(4-cyanovalerate
  • the above-mentioned polymerization initiators may be used alone or two or more kinds in combination.
  • the amount of the polymerization initiator is typically 0.001 to 5% by weight, relative to the total amount of the monomers.
  • the polymerization temperature is typically in the range of 0 to 120°C and more preferably in the range of 5 to 90°C.
  • the polymerization temperature is not required to be always kept constant and may be changed accordingly with the progress of the polymerization. Since the polymerization heat will usually generated with the progress of the polymerization to increase the polymerization temperature, cooling may be provided as needed.
  • the atmosphere during the polymerization is not particularly limited and the polymerization is preferably carried out, for example, under an inert gas atmosphere such as nitrogen gas, from the viewpoint of the smooth polymerization.
  • the polymerization time is not particularly limited and typically is in the range of 1 to 20 hours.
  • the pH of the solution during the polymerization is not particularly limited and the polymerization may be carried out by adjusting the pH as needed.
  • useful pH adjusters include alkalis such as sodium hydroxide, potassium hydroxide, ammonia; mineral acids such as phosphoric acid, sulfuric acid, hydrochloric acid; organic acids such as formic acid, acetic acid; and others.
  • the molecular weight of the polymer is not particularly limited and typically is in the range of 100,000 to 50, 000, 000 and preferably in the range of 500,000 to 30,000,000.
  • the amide-based polymer of the invention obtained in this way has a good balance between the water solubility and the high molecular weight, and is excellent in hue and may be preferably used as a flocculant, an additive for manufacturing paper, an oil recovery agent
  • the concentration of benzene was measured according to gas chromatographic analysis.
  • the gas chromatographic analysis was carried out by using G-950 1.2 mm ⁇ 40 m (25 ⁇ m) manufactured by Chemicals Evaluation and Research Institute, Japan as a column. Helium was used as a carrier gas and a FID detector was used for the analysis.
  • an adsorbent of an activated carbon fixed bed containing 1 kg of an activated carbon (internal surface area: 1000 m 2 /kg).
  • An acrylonitrile a having a concentration of benzene of 26 ppm was pumped through the adsorbent from the bottom to the top at a flow rate of 200 m/hr at a temperature of 1-0°C.
  • the concentration of benzene in the acrylonitrile was measured to be 4.0 ppm.
  • the acrylonitrile after the activated carbon absorption treatment is referred to as the acrylonitrile b.
  • Methacrylonitrile having a concentration of benzene of 8 ppm was used as it is.
  • a culture medium with a volume of 100 ml having the composition shown in the medium composition 1-1 was prepared in a 500-milliliter Erlenmeyer flask fitted with a baffle, and was sterilized in an autoclave at 121°C for 20 minutes. Thereafter, ampicillin was added to this medium so that the final concentration was 50 ⁇ g/ml. 30 flaskss were prepared in the same manner.
  • One loopful of MT-10822 strain (FERM BP-5785) was inoculated into each Erlenmeyer flask fitted with a baffle and the resultant medium was incubated at 37°C at 130 rpm for 20 hours.
  • Rhodococcus rhodochrous J-1 strain described in Japanese Unexamined Patent Application Publication No. H06-55148 (the strain deposited at the.above-mentioned deposition agency under an accession number FERM BP-1478, under the terms of the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure and is subdivided to all persons upon request).
  • a culture medium with a volume of 100 ml having the composition shown in the medium composition 1-2 was prepared into a 500-milliliter Erlenmeyer flask fitted with a baffle, and was sterilized in an autoclave at 121°C for 20 minutes. To this medium was inoculated one loopful of Rhodococcus rhodochrous J-1 strain described in Japanese Patent Application Publication No.
  • H06-55148 the strain deposited at the above-mentioned deposition agency under an accession number FERM BP-1478, under the terms of the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure and is subdivided to all persons upon request
  • incubated at 30°C at 130 rpm for 72 hours Only the microbial cell was separated from the culture solution through centrifugation (15000G ⁇ 15 minutes). Subsequently, the microbial cell was resuspended in 50 ml of a physiological saline solution and then the wet microbial cell was obtained through recentrifugation.
  • the wet microbial cell obtained in Preparation Example 1-1 was appropriately diluted with a 20 mM Tris-HCl buffer solution (pH 7.5). To the resulting solution was added the acrylonitrile b described in Production Example 1-1 so that the concentration of acrylonitrile in the whole reaction solution was 20% by weight and then the resultant mixture was reacted at 20°C for 10 minutes.
  • the concentration of benzene in the aqueous medium (I) (the whole reaction solution) was 0.8 ppm.
  • an equivalent weight of a 1 M phosphoric acid aqueous solution based on the reaction solution was added to the reaction solution to stop the reaction, and the concentration of the resulting acrylamide was measured by HPLC analysis.
  • the wet microbial cell obtained in Preparation Example 1-1 was appropriately diluted with a 20 mM Tris-HCl buffer solution (pH 7.5). To the resulting solution was added the acrylonitrile c described in Production Example 1-2 so that the concentration of acrylonitrile was 20% by weight and the resultant mixture was reacted at 20°C for 10 minutes. Here, the concentration of benzene in the aqueous medium (I) was 2.2 ppm. Thereafter, the procedures were performed in the same manner as in Example 1-1. The results are shown in Table 1-1.
  • the concentration of benzene in acrylonitrile was adjusted to be 20 ppm by adding benzene to the acrylonitrile b described in Production Example 1-1.
  • the procedures were performed in the same manner as in Example 1-1 except that the acrylonitrile to be used was replaced by the acrylonitrile as described above.
  • the concentration of benzene in the aqueous medium (I) was 4.0 ppm. The results are shown in Table 1-1.
  • Example 1-1 The procedures were performed in the same manner as in Example 1-1 except that the acrylonitrile to be used was replaced by the acrylonitrile a described in Production Example 1-1.
  • concentration of benzene in the aqueous medium (I) was 5.2 ppm.
  • Table 1-1 The results are shown in Table 1-1.
  • the concentration of benzene in acrylonitrile was adjusted to be 26 ppm by adding benzene to the acrylonitrile b described in Production Example 1-1.
  • the procedures were performed in the same manner as in Example 1-1 except that the acrylonitrile to be used was replaced by the acrylonitrile as described above.
  • the concentration of benzene in the aqueous medium (I) was 5.2 ppm. The results are shown in Table 1-1.
  • the decrease of reaction rate may be prevented by controlling the concentration of benzene in the aqueous medium (I) to 4.0 ppm or less and a substance causing the decrease of reaction rate is benzene.
  • Example 1-1 The procedures were performed in the same manner as in Example 1-1 except that the wet microbial cell to be used was replaced by the wet microbial cell obtained in Preparation Example 1-2. The results are shown in Table 1-2.
  • the reaction rate obtained was set as 100% and compared with those of Example 1-5 and Comparative Example 1-3, by setting the reaction rate obtained as 100%.
  • Example 1-2 The procedures were performed in the same manner as in Example 1-3 except that the wet microbial cell to be used was replaced by the wet microbial cell obtained in Preparation Example 1-2. The results are shown in Table 1-2.
  • the wet microbial cell obtained in Preparation Example 1-1 was appropriately diluted with a 20 mM Tris-HCl buffer solution (pH 7.5). To the resulting solution was added the methacrylonitrile described in Production Example 1-3 so that the concentration of methacrylonitrile was 20% by weight and the resultant mixture was reacted at 20°C for 10 minutes. Here, the concentration of benzene in the aqueous medium (I) was 1.6 ppm. After the reaction, an equivalent weight of a 1 M phosphoric acid aqueous solution based on the reaction solution was added to the reaction solution to stop the reaction, and the concentration of the resulting methacrylamide was measured by HPLC analysis.
  • the concentration of benzene in methacrylonitrile was adjusted to be 20 ppm by adding benzene to the methacrylonitrile described in Production Example 1-3.
  • the procedures were performed in the same manner as in Example 1-6 except that the methacrylonitrile to be used was replaced by the methacrylonitrile as described above.
  • the concentration of benzene in the aqueous medium (I) was 4.0 ppm. The results are shown in Table 1-3.
  • the concentration of benzene in methacrylonitrile was adjusted to be 25 ppm by adding benzene to the methacrylonitrile described in Production Example 1-3.
  • the procedures were performed in the same manner as in Example 1-6 except that the methacrylonitrile to be used was replaced by the methacrylonitrile as described above.
  • the concentration of benzene in the aqueous medium (I) was 5.0 ppm. The results are shown in Table 1-3.
  • Example 1-6 The procedures were performed in the same manner as in Example 1-6 except that the wet microbial cell to be used was replaced by the wet microbial cell obtained in Preparation Example 1-2. The results are shown in Table 1-4. The reaction rate obtained was set as 100% and compared with those of Example 1-9 and Comparative Example 1-5, by setting the reaction rate obtained as 100%.
  • Example 1-7 The procedures were performed in the same manner as in Example 1-7 except that the wet microbial cell to be used was replaced by the wet microbial cell obtained in Preparation Example 1-2. The results are shown in Table 1-4.
  • a microbial cell containing a nitrile hydratase was cultured and the resulting wet microbial cell was suspended in a 0.3 mM-NaOH aqueous solution.
  • the suspension and the acrylonitrile b were continuously fed into the first reactor under stirring at a rate of 49 g/h and 31 g/h, respectively.
  • the reaction solution was continuously taken out from the first reactor at a rate of 80 g/h so that the liquid level of the first reactor was maintained constant.
  • the liquid taken out was continuously fed into the second reactor at a rate of 80 g/h and the reaction was further performed in the second reactor.
  • Both the first and second reactors were immersed in a water bath at a temperature of 10 to 20°C to control the liquid temperature in each reactor at 15°C.
  • the amount of the wet microbial cell added to the 0.3 mM-NaOH aqueous solution was adjusted so that the conversion rate to acrylamide at the outlet of the first reactor was 90% or higher and the concentration of acrylonitrile at the outlet of the second reactor was at the detection limit or less (100 ppm or less).
  • the conversion rate to acrylamide was determined by the analysis of HPLC.
  • the objective conversion rate was achieved when the wet microbial cell was 2.5% by weight based on the 0.3 mM-NaOH aqueous solution.
  • Example 1-10 The procedures were performed in the same manner as in Example 1-10 except that the acrylonitrile to be used was replaced by the acrylonitrile a.
  • the added amount of the wet microbial cell required for achieving the objective conversion rate was 3.0% by weight of the wet microbial cell based on the 0.3 mM-NaOH aqueous solution.
  • the added amount of the wet microbial cell was larger than that in the case of Example 1-10 and the inhibition of reaction by benzene was confirmed.
  • the concentration of benzene in acrylonitrile was adjusted to be 26 ppm by adding benzene to the acrylonitrile b.
  • the procedures were performed in the same manner as in Example 1-10 except that the acrylonitrile to be used was replaced by the acrylonitrile as described above.
  • the added amount of the wet microbial cell required for achieving the objective conversion rate was 3.0% by weight of the microbial cell based on the 0.3 mM-NaOH aqueous solution.
  • the added amount of the wet microbial cell was larger than that in the case of Example 1-10 and the inhibition of reaction by benzene was confirmed.
  • Example 1-10 The reaction solution of Example 1-10 was treated with an activated carbon under acidic conditions (pH 5), and then the wet microbial cell was removed. The resulting reaction solution was neutralized with 1 N-NaOH to obtain an aqueous solution of 50% by weight of acrylamide.
  • the feeding of nitrogen gas was stopped because the internal temperature of the polyethylene vessel was observe to rise.
  • the polyethylene vessel was kept as it is in the heat-insulating block for approximately 100 minutes, and consequently the internal temperature of the polyethylene vessel reached approximately 70°C.
  • the polyethylene vessel was then taken out from the heat-insulating block and immersed in waster at 97 °C for 2 hours to further perform the polymerization reaction. Thereafter, the polyethylene vessel was immersed in cold water to cool and stop the polymerization reaction.
  • the thus obtained water-containing gel of an acrylamide polymer was taken out from the polyethylene vessel, divided into small pieces, and ground through a mincer.
  • the ground water-containing gel of the acrylamide polymer was dried with hot air at 100°C for 2 hours and further ground by a high-speed rotary blade grinder to obtain a dried powderly acrylamide polymer.
  • the resulting dried powderly acrylamide polymer was sieved to collect the powder that passed through 32- to 42-mesh screens. Thus, a polymer sample for a subsequent test was obtained.
  • Example 1-11 In the same manner as in Example 1-11, an aqueous solution of 20% by weight of acrylamide was obtained from the reaction solution obtained in Comparative Example 1-6, and a polymer sample was obtained by using the aqueous solution of the acrylamide.
  • Example 1-11 In the same manner as in Example 1-11, an aqueous solution of 20% by weight of acrylamide was obtained from the reaction solution obtained in Comparative Example 1-7, and a polymer sample was obtained by using the aqueous solution of the acrylamide.
  • the present invention is useful for industrially performing the production of the amide compound.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Genetics & Genomics (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Biotechnology (AREA)
  • Biochemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Molecular Biology (AREA)
  • Biomedical Technology (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (8)

  1. Procédé de production d'un composé amide, dans lequel le procédé comprend l'étape préliminaire consistant à traiter un composé nitrile avec du charbon actif, et le procédé comprend en outre l'étape consistant à produire le composé amine à partir du composé nitrile obtenu par un traitement avec du charbon actif, dans lequel la production du composé amine à partir du composé nitrile s'effectue dans un milieu aqueux en présence d'un catalyseur ayant une activité nitrile hydratase, dans lequel la concentration de benzène dans le milieu aqueux est de 4 ppm ou moins.
  2. Procédé selon la revendication 1, dans lequel la nitrile hydratase est une nitrile hydratase dérivée de Pseudonocardia ou une nitrile hydratase dérivée de Rhodococcus.
  3. Procédé selon la revendication 1 ou 2, dans lequel le composé nitrile est de l'acrylonitrile ou du méthacrylonitrile.
  4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel le composé amide est de l'acrylamide ou de la méthacrylamide.
  5. Procédé de production d'un polymère à base d'amide, comprenant :
    une étape préliminaire consistant à traiter un composé nitrile avec du charbon actif ;
    la production d'un composé amine à partir du composé nitrile obtenu par le traitement avec du charbon actif, et dans lequel la production du composé amine à partir du composé nitrile s'effectue dans un milieu aqueux en présence d'un catalyseur ayant une activité nitrile hydratase, dans lequel la concentration de benzène dans le milieu aqueux est de 4 ppm ou moins ; et
    l'homopolymérisation du composé amide, ou la copolymérisation du composé amide et d'au moins un monomère insaturé copolymérisable avec le composé amide.
  6. Procédé selon la revendication 5, dans lequel la nitrile hydratase est une nitrile hydratase dérivée de Pseudonocardia ou une nitrile hydratase dérivée de Rhodococcus.
  7. Procédé selon la revendication 5 ou 6, dans lequel le composé nitrile est de l'acrylonitrile ou du méthacrylonitrile.
  8. Procédé selon l'une quelconque des revendications 5 à 7, dans lequel le composé amide est de l'acrylamide ou de la méthacrylamide.
EP06811414.9A 2005-10-07 2006-10-06 Procédé de production d'un composé amide Active EP1944376B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP16187709.7A EP3135767B1 (fr) 2005-10-07 2006-10-06 Procédé de production d'acrylamide

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2005295561 2005-10-07
JP2005375024 2005-12-27
PCT/JP2006/320087 WO2007043466A1 (fr) 2005-10-07 2006-10-06 Procédé de production d’un composé amide

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP16187709.7A Division-Into EP3135767B1 (fr) 2005-10-07 2006-10-06 Procédé de production d'acrylamide
EP16187709.7A Division EP3135767B1 (fr) 2005-10-07 2006-10-06 Procédé de production d'acrylamide

Publications (3)

Publication Number Publication Date
EP1944376A1 EP1944376A1 (fr) 2008-07-16
EP1944376A4 EP1944376A4 (fr) 2012-03-14
EP1944376B1 true EP1944376B1 (fr) 2016-11-30

Family

ID=37942709

Family Applications (2)

Application Number Title Priority Date Filing Date
EP16187709.7A Active EP3135767B1 (fr) 2005-10-07 2006-10-06 Procédé de production d'acrylamide
EP06811414.9A Active EP1944376B1 (fr) 2005-10-07 2006-10-06 Procédé de production d'un composé amide

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP16187709.7A Active EP3135767B1 (fr) 2005-10-07 2006-10-06 Procédé de production d'acrylamide

Country Status (7)

Country Link
US (2) US20090171051A1 (fr)
EP (2) EP3135767B1 (fr)
JP (2) JP4970276B2 (fr)
KR (2) KR20110038183A (fr)
CN (1) CN102911973A (fr)
AU (1) AU2006300431B2 (fr)
WO (1) WO2007043466A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105247063B (zh) * 2012-12-10 2020-10-23 三菱化学株式会社 丙烯酰胺的制造方法
US9382560B2 (en) 2013-02-19 2016-07-05 Mitsubishi Rayon Co., Ltd. Method for producing amide compound
JP6020741B1 (ja) * 2014-12-17 2016-11-02 三菱レイヨン株式会社 アクリルアミド水溶液及びアクリルアミド系重合体の製造方法
CN106148312A (zh) * 2015-04-15 2016-11-23 四川光亚聚合物化工有限公司 稳定贮存微生物法生产丙烯酰胺发酵液酶活性的方法
BR112018069317A2 (pt) * 2016-03-29 2019-01-22 Basf Se métodos para produzir uma solução de poliacrilamida com viscosidade aumentada e para preparar uma solução de poliacrilamida, uso de uma solução aquosa de acrilamida, solução aquosa de acrilamida, poliacrilamida, e, método para produzir uma solução de poliacrilamida
WO2017186685A1 (fr) * 2016-04-26 2017-11-02 Basf Se Procédé de préparation d'une solution aqueuse de polyacrylamide
EP3448898A1 (fr) * 2016-04-26 2019-03-06 Basf Se Procédé de préparation d'une solution aqueuse de polyacrylamide
AU2017257205A1 (en) * 2016-04-26 2018-10-18 Basf Se Method for preparing an aqueous polyacrylamide solution
AU2019243341B2 (en) * 2018-03-28 2021-09-23 Mitsui Chemicals, Inc. Method for producing amide compound
JP2019176835A (ja) * 2018-03-30 2019-10-17 三井化学株式会社 アミド化合物の製造方法
JP2023523337A (ja) * 2019-12-30 2023-06-02 ケミラ・ユルキネン・オサケユフティオ アクリルアミド合成の反応監視のためのｆｔｎｉｒ分光法
WO2024004661A1 (fr) * 2022-06-30 2024-01-04 三井化学株式会社 Nitrile hydratase de type modifié ainsi que procédé de fabrication de celle-ci, acide nucléique codant cette nitrile hydratase de type modifié, vecteur ainsi que transformant contenant cet acide nucléique, et procédé de fabrication de composé amide

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6043061A (en) * 1997-10-23 2000-03-28 Mitsubishi Rayon Co., Ltd. Process for producing amide compound

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2622097A (en) * 1950-11-13 1952-12-16 American Cyanamid Co Purification of acrylonitrile
JPS5268118A (en) * 1975-11-21 1977-06-06 Mitsui Toatsu Chem Inc Preparation of acrylamide
JPS581108B2 (ja) * 1978-05-22 1983-01-10 三井東圧化学株式会社 アクリロニトリルの精製法
US4177210A (en) 1978-07-05 1979-12-04 The Dow Chemical Company Hydration of acrylonitrile to acrylamide
GB2114118A (en) * 1982-01-29 1983-08-17 American Cyanamid Co Method for removing aldehyde impurities in acrylonitrile and acrylamide
JPS61115495A (ja) * 1984-11-09 1986-06-03 Nitto Chem Ind Co Ltd アクリルアミド系重合体の製造方法
JPH05308980A (ja) 1992-05-07 1993-11-22 Mitsubishi Kasei Corp アミド類の製造法
US5426208A (en) 1992-05-21 1995-06-20 Cryodyne Technologies, Inc. Method of purification of acetonitrile
ATE148102T1 (de) * 1992-05-21 1997-02-15 Cryodyne Tech Inc Verfahren zur reinigung von acetonitril
JPH0655148A (ja) 1992-08-06 1994-03-01 Hitachi Ltd ガラス基板洗浄装置
JP3683916B2 (ja) * 1993-07-23 2005-08-17 三井化学株式会社 アクリルアミドの製造方法
US5476883A (en) * 1993-07-23 1995-12-19 Mitsui Toatsu Chemicals, Inc. Preparation process of acrylamide from purified acrylonitrile
JP3521474B2 (ja) 1994-03-30 2004-04-19 ダイヤニトリックス株式会社 アミド化合物の製造法
JPH07265091A (ja) 1994-03-30 1995-10-17 Mitsubishi Chem Corp アミド化合物の製造法
JP3642590B2 (ja) * 1994-12-06 2005-04-27 三井化学株式会社 アクリロニトリルの精製方法
US5552305A (en) * 1995-03-30 1996-09-03 E. I. Du Pont De Nemours And Company Biocatalytic conversion of azobisnitriles to cyanoamides or diamides using Pseudomonas, Rhodococcus or Brevibacterium
JP3908803B2 (ja) * 1996-02-20 2007-04-25 三井化学株式会社 アクリルアミドの製造方法
JPH10316714A (ja) * 1997-05-15 1998-12-02 Mitsubishi Rayon Co Ltd アクリルアミド系重合体の製造方法
US6153415A (en) * 1998-04-29 2000-11-28 Board Of Trustees Operating Michigan State University Method for producing amide compounds using a nitrile hydratase from a thermophilic bacillus
US6074532A (en) * 1998-11-05 2000-06-13 Nalco/Exxon Energy Chemicals, L.P. Adjunct for removal of aldehydes from chemical manufacturing production streams during distillative purification
JP4959059B2 (ja) * 2000-01-17 2012-06-20 三井化学株式会社 アミド化合物の精製方法
US7700330B2 (en) * 2000-01-17 2010-04-20 Mitsui Chemicals, Inc. Method of purifying amide compound
JP4672161B2 (ja) 2000-03-29 2011-04-20 三井化学株式会社 アミド化合物の製造方法
JP2002080443A (ja) * 2000-06-20 2002-03-19 Mitsubishi Chemicals Corp アクリロニトリル組成物およびその製造方法
KR100815093B1 (ko) * 2000-07-18 2008-03-20 더 스탠다드 오일 캄파니 아세토니트릴의 정제 및 회수의 개선 방법
US7749739B2 (en) * 2000-12-20 2010-07-06 Dia-Nitrix Co., Ltd. Process for producing amide compound using microbial catalyst
US20070027294A1 (en) * 2003-04-10 2007-02-01 Dia-Nitrix Co., Ltd. Process for producing high-quality acrylamide polymer with enzyme
JP4389064B2 (ja) 2003-05-28 2009-12-24 三井化学株式会社 ニトリルヒドラターゼ活性を維持または向上させる方法
AU2004295409B2 (en) 2003-12-02 2010-07-29 Ciba Specialty Chemicals Water Treatments Limited Strain of Rhodococcus rhodochrous NCIMB 41164 and its use as producer of nitrile hydratase

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6043061A (en) * 1997-10-23 2000-03-28 Mitsubishi Rayon Co., Ltd. Process for producing amide compound

Also Published As

Publication number Publication date
EP1944376A1 (fr) 2008-07-16
KR20080056261A (ko) 2008-06-20
AU2006300431A1 (en) 2007-04-19
US20110288255A1 (en) 2011-11-24
WO2007043466A9 (fr) 2007-06-14
JP2012029695A (ja) 2012-02-16
WO2007043466A1 (fr) 2007-04-19
AU2006300431B2 (en) 2011-07-21
EP3135767B1 (fr) 2020-12-02
EP3135767A1 (fr) 2017-03-01
KR20110038183A (ko) 2011-04-13
JP4970276B2 (ja) 2012-07-04
CN102911973A (zh) 2013-02-06
EP1944376A4 (fr) 2012-03-14
US20090171051A1 (en) 2009-07-02
US8329843B2 (en) 2012-12-11
JPWO2007043466A1 (ja) 2009-04-16

Similar Documents

Publication Publication Date Title
EP1944376B1 (fr) Procédé de production d'un composé amide
US8143033B2 (en) Process for producing (meth)acrylamide
JP5430659B2 (ja) 菌体処理物の製造方法
EP2006390B1 (fr) Procédé de production d'acrylamide
AU2011239258B2 (en) Method for producing amide compound
JP4975735B2 (ja) アクリルアミドの製造方法
JP2008247979A (ja) 高品質の（メタ）アクリルアミド系重合体の製造方法
KR20080099323A (ko) (메타)아크릴아미드의 제조방법
JP2008138089A (ja) 高品質の（メタ）アクリルアミド系重合体の製造方法
JP2016202030A (ja) （メタ）アクリルアミドの製造方法、（メタ）アクリルアミド系重合体および（メタ）アクリルアミド系重合体の製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080425

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB NL

RBV Designated contracting states (corrected)

Designated state(s): DE FR GB NL

A4 Supplementary search report drawn up and despatched

Effective date: 20120215

RIC1 Information provided on ipc code assigned before grant

Ipc: C08F 20/56 20060101ALI20120209BHEP

Ipc: C12P 13/02 20060101AFI20120209BHEP

Ipc: C07C 233/09 20060101ALI20120209BHEP

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20151006

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160502

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602006051096

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602006051096

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

26N No opposition filed

Effective date: 20170831

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20231019

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231020

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20231023

Year of fee payment: 18

Ref country code: DE

Payment date: 20231020

Year of fee payment: 18